An Imidazolylidene‐Based Mesoionic Carbene–Mn(I) Complex and Its Catalytic Potential in N‐Heteroarene Hydrogenation DOI Open Access
Ravi Kumar, Madhusudan K. Pandey,

Indresh Kumar Pandey

et al.

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 26(29)

Published: Aug. 10, 2023

Abstract Herein we report the first mesoionic carbene (MIC)‐Mn(I) complex Mn‐bim‐MIC imz derived from imidazolylidene motif. Structurally octahedral Mn(I) was assembled with an anionic benzimidazolato‐anchored MIC‐based bidentate ligand ( bim‐MIC ) and four CO ligands, as supported by detailed characterization using NMR FTIR spectroscopy, mass spectrometry, single crystal X‐ray diffraction study. We reckoned that would provide a robust stable bonding centre, also enhance electron density at centre through its stronger σ‐donating/weaker π‐accepting property. These structural electronic attributes triggered to exploit in catalytic hydrogenation of N‐heteroarenes, where efficient hydride (Mn−H) delivery is key step.

Language: Английский

Nanoarchitectonics of Non-Noble-Metal-Based Heterogeneous Catalysts for Transfer Hydrogenation Reactions: Detailed Insights on Different Hydrogen Sources DOI
Devendra Sharma, Priyanka Choudhary,

Prerna Mittal

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4211 - 4248

Published: March 5, 2024

Catalytic transfer hydrogenation (CTH) methodology has drawn profound attention of researchers as an economical and environmentally benign alternate to conventional method. Unlike method, CTH exhibits better reaction efficiency atom economy, it makes use simple, easily accessible, low-cost hydrogen sources. Current research on reactions is oriented toward the development non-noble-metal-based catalysts due their high abundance potential large-scale applicability. In this Review, different organic transformation reactions, such nitroarenes, nitriles, alkenes, alkynes, carbonyl compounds, hydrogenolysis, reductive amination, formylation using sources have been summarized comprehensively. addition, synthesis strategies heterogeneous structure–activity relationship involving metal–support interaction, single-atom catalysis, synergistic effect are highlighted. Furthermore, optimization parameters─such temperature, time, solvents, additives─for enhancing catalytic activity selectivity product discussed in detail. This Review provides detailed insights into recent progress made with a specific focus catalyst development, sources, mechanistic exploration.

Language: Английский

Citations

39
Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations DOI Creative Commons
Dexin Fu, Zheng Wang, Qingbin Liu

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(14)

Published: March 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Language: Английский

Citations

11
Bis(N‐Heterocyclic Carbene) Manganese(I) Complexes: Efficient and Simple Hydrogenation Catalysts DOI Creative Commons
Niklas F. Both,

Anke Spannenberg,

Haijun Jiao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(35)

Published: July 3, 2023

The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation esters was investigated. For that purpose, a series has been synthesized via an improved two step procedure utilizing bis(NHC)-BEt3 adducts. By applying with KHBEt3 additive, various aromatic and aliphatic were hydrogenated successfully at mild temperatures low catalyst loadings, highlighting efficiency novel catalytic system. versatility developed system further demonstrated by other substrate classes like ketones, nitriles, N-heteroarenes alkenes. Mechanistic experiments DFT calculations indicate inner sphere mechanism loss one CO ligand reveal role BEt3 cocatalyst.

Language: Английский

Citations

18
Highly efficient transfer dehydrogenative oxidation of secondary alcohols to ketones catalyzed by NN-manganese complexes DOI
Zheng Wang,

Xiaochi Lu,

Zhihui Li

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 430, P. 115337 - 115337

Published: Feb. 1, 2024

Language: Английский

Citations

9
Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation DOI Creative Commons

Ekaterina S. Gulyaeva,

Ruqaya Buhaibeh, Mohamed Boundor

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(22)

Published: Feb. 7, 2024

Abstract Systematic modification of the chelating NHC‐phosphine ligand (NHC = N ‐heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac ‐[(Ph 2 PCH NHC)Mn(CO) 3 Br] has been performed and catalytic activity resulting complexes was evaluated using acetophenone as a benchmark substrate. While variation phosphine NHC moieties led to inferior results than for parent system, incorporation phenyl substituent into methylene bridge improved performance by ca . times providing maximal TON values range 15000–20000. Mechanistic investigation combining experimental computational studies allowed rationalize this beneficial effect an enhanced stabilization reaction intermediates including anionic hydride species PC(Ph)NHC)Mn(CO) H] − playing crucial role process. These highlight interest such carbon substitution strategy being rarely employed design chemically non‐innocent ligands.

Language: Английский

Citations

6
Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory Exploration DOI Creative Commons
María Gutiérrez‐Blanco, Andrés G. Algarra, Eva Guillamón

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(2), P. 1000 - 1009

Published: Jan. 4, 2024

Semihydrogenation of internal alkynes catalyzed by the air-stable imidazolyl amino [Mo

Language: Английский

Citations

5
Hydrogenation of N-Heterocycles by a Well-Defined Phosphine-Free Manganese Catalyst Using Ammonia Borane DOI
Ankur Maji, Shivangi Gupta, Dibyajyoti Panja

et al.

Organometallics, Journal Year: 2023, Volume and Issue: 42(23), P. 3385 - 3396

Published: Nov. 27, 2023

Efficient hydrogenation of N-heterocycles employing low-cost and easy-to-access catalysts is highly desirable as the corresponding hydrogenated have significant importance. Herein, we disclosed well-defined phosphine-free Mn-catalyzed effective transfer (TH) various using ammonia borane hydrogen source. In this work, a series Mn(I) complexes were synthesized to investigate importance ligand backbone containing benzimidazole N–H, amine soft sulfur atom. Reactivity studies these Mn revealed that proton-responsive Mn1 complex bearing N–H proton benzimidazole, amine, hemilabile arm was found be most effective. The capability procedure verified by synthesis several biologically active compounds. Mechanistic pathways established performing control reactions kinetic experiments.

Language: Английский

Citations

11
Recent Advances in Nonprecious Metal Catalysis DOI
Andrew R. Ickes, Michael C. Haibach, Nicholas G. W. Cowper

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 937 - 948

Published: March 21, 2024

Significant emphasis has been placed on the development of nonprecious metal alternatives to precious-metal-catalyzed reactions due lower cost and greater sustainability they can achieve. This review is part a series describing advances in nonprecious-metal-catalyzed transformations published between March June 2023 that are relevant pharmaceutical process chemistry.

Language: Английский

Citations

3
Amplifying the Reactivity of Anionic Mn(I)–H Catalysts via the Cation Effect: Mechanistic Investigation and Application to the Hydrogenation of α-Trisubstituted Carboxylic Esters DOI
Haobo Yang, Shihan Liu, Hao Dong

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Despite significant advancements in ester hydrogenation using homogeneous metal catalysts over the past two decades, catalytic of sterically hindered α-trisubstituted carboxylic esters remains a formidable challenge. Herein, we present class imidazole-based NNP-pincer manganese (Mn) capable efficiently hydrogenating to their corresponding β-trisubstituted primary alcohols, which are widely applied pharmaceutical and fine-chemical industry. Under conditions, imidazole moiety is deprotonated by tBuOK generate highly reactive anionic Mn-H species with potassium countercation. Mechanistic studies reveal that cation this intermediate interacts synergistically substrate's carbonyl group alkoxide during hydrogen activation. This effect significantly lowers energy barriers for both hydride transfer heterolytic H2 cleavage, thereby enhancing activity. Leveraging potent catalyst, achieved diverse array carboxylates (80 examples) under mild conditions.

Language: Английский

Citations

0
Manganese‐Catalysed Transfer Hydrogenation of Quinolines under Mild Conditions DOI
Xiaoxiao Chu, Guoren Zhou, Maofu Pang

et al.

European Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: unknown

Published: Aug. 29, 2023

Abstract Herein, an efficient methodology for the homogeneous manganese‐catalysed transfer hydrogenation of N‐heterocycles by using ammonia‐borane as a hydrogen source under mild reaction conditions is reported. Good to excellent isolated yields are achieved applying PNP manganese pincer complex. In reaction, 1,2‐dihydroquinoline detected intermediate NMR spectra analysis and deuterium labelling experiment. The catalytic likely proceeded outer‐sphere pathway based on bifunctional

Language: Английский

Citations

8